Biochar Compositions and Methods of Use Thereof

ABSTRACT

The invention provides for methods, devices, and systems for pyrolyzing biomass. A pyrolysis unit can be used for the pyrolysis of biomass to form gas, liquid, and solid products. The biomass materials can be selected such that an enhanced biochar is formed after pyrolysis. The biomass can be pyrolyzed under specified conditions such that a selected biochar core is formed. The pyrolysis process can form a stable biochar core that is inert and/or resistant to degradation. The biochar or biochar core can be functionalized to form a functionalized biochar or functionalized biochar core. Functionalized can include post-pyrolysis treatments such as supplementation with microbes or physical transformations including annealing and/or activation.

CROSS-REFERENCE

This application is a continuation application of application Ser. No.16/180,884 filed on May 11, 2018 for Biochar Compositions and Methods ofUse Thereof, which in turn is a continuation of application Ser. No.15/667,050 filed Aug. 2, 2017 for Biochar Compositions and Methods ofUse Thereof, which in turn is a continuation of application Ser. No.14/506,503 filed on Oct. 3, 2014 for Biochar Compositions and Methods ofUse Thereof which in turn is a US national phase application of PCTUS2013/035529, filed Apr. 5, 2013, which claims the benefit of U.S.Provisional Application No. 61/620,949, filed Apr. 5, 2012, each ofwhich application is entirely incorporated herein by reference.

BACKGROUND OF THE INVENTION

Increasing agricultural production in a sustainable way and mitigatingthe effects of climate change are two of the most important challengesfacing the modern world. These challenges include a need for higher cropyields, a need to make degraded soils more productive, and a need tomanage for productive agriculture with less dependable water resources.Some efforts have been made to reduce the long-term negative effects ofagriculture by crop-rotation and organic fanning. Efforts have been madeto address climate change by reducing avoidable greenhouse gas emissionsthrough production of renewable energy and off-setting unavoidableemissions through sequestration of carbon in the environment. Somecarbon sequestration efforts have been aimed at storage of carbon insoil and of carbon dioxide in geologic formations. However, due to theinherent lack of long-term stability of plant derived biomass storage ofcarbon derived directly from plant biomass is not a long-term solution.Pyrolysis of biomass to produce a solid material called char, charcoalor more specifically biochar, which can be a product that is tailoredfor use as a soil amendment, can play a significant role in both ofthese efforts related to climate change and agriculture, but iscurrently limited by the use of biochars that exhibit instability ordegradation and which may have positive or negative effects on soilflora, fauna and or plant growth. Therefore, there is a need forimproved methods, devices, and systems for the production of stableand-or beneficial biochars.

SUMMARY OF THE INVENTION

The invention provides for methods, devices, and systems for pyrolyzingbiomass and producing enhanced and/or functionalized biochar. Apyrolysis unit can be used for the pyrolysis of biomass to form gas,liquid, and solid products. The biomass can be pyrolyzed under specifiedconditions such that a selected biochar core, also referred to asbiocore elsewhere herein, is formed. The pyrolysis process can form astable biochar core that is inert and/or resistant to degradation.

One aspect of the invention provides for a method for producing aselected type of biochar core comprising the steps of introducing abiomass feedstock to a pyrolysis unit and pyrolyzing the biomass in thepyrolysis unit in accordance with a predetermined set of operatingparameters attuned to the selected biomass feedstock to produce dieselected type of biochar core. The predetermined set of operatingparameters can include, pre or post pyrolysis treatments of biochar aswell as an established temperature range and rate of temperature changethat corresponds to the selected type of biochar core. The inventionalso provides for systems and methods that include pre and/or postpyrolysis treatments of biochars.

Another aspect of the invention provides for the production of enhancedand/or functionalized biochar. Enhanced biochar can be produced byblending, mixing, other otherwise combining selected feed materials suchthat a selected biochar is formed by pyrolysis. Functionalized biocharcan include, for example a biocore that has been supplemented with amicrobe or a nutrient or an organic substance.

INCORPORATION BY REFERENCE

All publications, patents, and patent applications mentioned in thisspecification are herein incorporated by reference to the same extent asif each individual publication, patent, or patent application wasspecifically and individually indicated to be incorporated by reference.

BRIEF DESCRIPTION OF THE DRAWINGS

The novel features of the invention are set forth with particularity inthe appended claims. A better understanding of the features andadvantages of the present invention will be obtained by reference to thefollowing detailed description that sets forth illustrative embodiments,in which the principles of the invention are utilized, and theaccompanying drawings of which:

FIG. 1 shows a diagram of a process for producing an enhanced biochar.

FIG. 2 shows a diagram of a process for producing a functionalizedbiochar.

FIG. 3 is a graph showing pH adjustment of biochar.

FIG. 4 is a graph depicting the effects of treating biochar with awetting agent.

FIG. 5 is a graph depicting the aeration and water holdingcharacteristics of various biochar blends.

FIG. 6 is a graph depicting electrical conductivity of biochar ascompared to other compositions.

FIG. 7 is a schematic showing four different distributions of biochar orbiochar blend used in a raised bed or in conjunction with an irrigationsystem.

INCORPORATION BY REFERENCE

All publications and patent applications mentioned in this specificationare herein incorporated by reference to the same extent as if eachindividual publication or patent application was specifically andindividually indicated to be incorporated by reference.

DETAILED DESCRIPTION OF THE INVENTION

The invention provides for methods, devices, and systems for pyrolyzingbiomass. A pyrolysis unit can be used for the pyrolysis of biomass toform gas, liquid, and solid products. The gas, liquid, and solidproducts can be syngas (the non-condensable, permanent gases includingCO, CO.sub.2, CH.sub.4, H.sub.2 and higher hydrocarbons of formulaC.sub.xH.sub.y which can be gaseous at 20.degree. C. and atmosphericpressure), bio-oil (also referred to as pyrolysis liquids, pyroligneousacid, bio-fuel-oil pyrolysis tars), and char, charcoal, biocarbon,agrichar, biochar, enhanced biochar, or biocore (also referred to asbiochar core elsewhere herein), respectively.

As shown in FIG. 1, selected biomass materials, can be pyrolysed atspecified pyrolysis conditions to form a selected enhanced biochars. Theselection of biomass materials and/or the specified pyrolysis conditionscan be altered to produce a variety of enhanced biochars that can betailored to a variety of applications, described herein.

As shown in FIG. 2, selected biomass materials can be pyrolyzed underspecified conditions such that one or more selected biocores are formed.The pyrolysis process can form one or more stable biocores that areinert and/or resistant to degradation. The biocores can be configured,for example by blending with a supplement, for use as a soil amendment,as a potting mix, as a substitute in a growing media (including peatand/or compost media), as a horticultural media, as a carbonsequestration agent, a mitigant for soil greenhouse gas emissions, afertilizing agent, a landscaping amendment, a turfgrass establishment, abioremediation agent, a delivery agent for fungi or bacterialpopulations, or any combination thereof and not limited to thesupplements listed. The biochar cores can be further tailored, enhancedand/or functionalized using a variety of methods, systems and processesdescribed herein In some embodiments of the invention, the biocores canbe tailored, enhanced, and/or functionalized to a particular end use orapplication.

I. Biomass

The biomass used for formation of pyrolysis products can be obtainedfrom a variety of sources. The biomass can be any material containingorganic carbon. For example, the biomass can be plant material,cellulosic materials. Iignin containing material, animal by-products,organic wastes, landfill matter, marine waste, agricultural waste,animal or human waste, other naturally derived sources of carbon, or anycombination thereof. The biomass materials can also include compost,sewage sludge, or vinasse. Biomass materials can be blended to form abiomass feedstock. For example, biomass obtained from a softwood (e.g.,a pine tree) or a hardwood (e.g., and oak tree) can be blended withpoultry litter and then pyrolyzed. In some embodiments, metals or otherchemicals can be blended with the biomass prior to pyrolysis. Examplesof the pyrolysis of poultry litter and animal waste are described inJP2001252558, U.S. Pat. No. 6,189,463 and U.S. Patent Publication No.2009/0031616, each of which are incorporated herein by reference.

In some embodiments of the invention, the biomass is selected based onthe chemical content of the material, the elemental composition of thebiomass, or the content of its elemental composition. For example, abiomass can be selected on its content of carbon, hydrogen, oxygen,nitrogen, phosphorous, potassium, selenium, cobalt, iron, manganese orany combination thereof in the biomass and any other elements. Thebiomass can be selected based on the content of water, oil,hydrocarbons, volatile compounds, organic carbon, volatile organiccarbons, or any combination thereof. Any of these content parameters canbe selected to be higher, lower, or up to about 1, 5, 10, 15, 20, 25,30, 40, 50, 60, 70, 80, 85, 90, 95, or 99% by weight or volume.

In some embodiments of the invention, the biomass feedstock can beselected based on the energy content of the biomass materials. Theenergy content of the biomass feedstock, determined by the biomassmaterials used, can be at least, up to, greater than, or less than about1, 5, 10, 15, 20, 25, or 30 GJ/ton, which can be measured on a dry (suchas atmospheric or oven dry) weight or dry ash-free basis. In someembodiments of the invention, the biomass feedstock can be elected basedon the particle size and shape of the biomass materials. The particlesize and shape of the biomass feedstock can be controlled by cutting,crushing, grinding, screening or breaking of a biomass material. Forexample, trees can be chipped and/or ground to a particular particlesize and then fed to a pyrolysis unit.

Selection of the biomass feedstock can allow for the formation ofpredetermined pyrolysis products. For example, a biomass feedstock canbe formed from and crop such as switchgrass or miscanthus or a cropby-product such as corn stover and a biomass material with high nutrientcontent, such as manure or rapemeal, to form a biochar that may be usedas a nutrient source. As another example, wood or high ash feedstocks(including feedstocks having greater than about 5% ash) can besupplemented to a biomass material to enhance the production of liquidpyrolysis products.

Pretreatment of biomass can relate to physical preparation of thebiomass-drying (air. steam, warm exhaust gases or other), size reduction(milling, grinding, chopping, shredding), screening to a certain sizefraction, or range of size fractions. Biomass can also be pretreated bythe addition of elements and/or compounds, reacted with chemicals toreduce or remove any of the biomass constituents (including acidwashing, alkali treatment, hot water washing, cold water washing, steamexposure, washing with an organic solvent, dissolution in ionicliquids). Biomass can also be thermally treated after drying to reduceits degree of polymerization, remove volatile compounds and/orextractives. This process can sometimes be called conditioning ortorrefaction. In some embodiments of the invention, conditioning ortorrefaction can be performed at temperatures lower than typicalpyrolysis temperatures.

The biomass materials can be selected such that the pyrolysis productsinclude an enhanced biochar or enhanced biochar core. The enhancedbiochar or biochar core can be used for a variety of applications,including any application described herein. The enhanced biochar orbiochar core can also be functionalized to form 2 functionalized and/orenhanced biochar core.

The invention also provides for a method for producing biochar withunique characteristics that enable the source of a biochar to be known.Feedstock materials with distinct C12:C13 isotope ratios can be used toproduce biochar core with a distinct C12:C13 signal. Hie biochar corewith distinct C12:C13 can then be introduced to a soil with a known anddifferent C12:C13 ratio. The feedstock materials with distinct C12:C13isotope ratios can be blended to produce biochar core with a distinctC12:C13 signal that is not naturally occurring. In some embodiments, thebiochar can be produced using a predetermined set of operatingparameters. The predetermined set of operating parameters can include atime-dependent temperature profile to produce a biochar core withdistinct characteristic that can be measured by thermogravimetricanalysis (TGA). In some embodiments, salts are added to feedstock priorto pyrolysis in order to produce material with a defined set ofproperties. In other embodiments, salts are introduced during pyrolysisin order to produce biochar with a defined set of properties.

II. Pyrolysis

The invention provides for a pyrolysis unit that can be used forformation of pyrolysis products from a biomass feedstock. The pyrolysisunit can control the pyrolysis conditions of the biomass feedstock suchthat selected types of pyrolysis products are formed. In someembodiments of the invention, a selected type of biochar core is formedfrom a selected biomass feedstock. The biochar core can be a stablebiochar core that is inert and/or resistant to degradation, for examplemicrobial, biological, chemical, thermal and/or oxidative degradation.The pyrolysis unit can be a gasifier or reactor, as described in U.S.Pat. Nos. 6,830,597 and 6.902,711, each of which are incorporated hereinby reference in their entirety. Solid pyrolysis products, includingbiochar, that can be formed using the methods and devices describedherein can also be referred to as pyrolysis char, charcoal, bio-carbon,or other similar names.

The pyrolysis unit can be operated in a batch, continuous, orsemi-continuous mode. A biomass feedstock can be supplied or introducedto the pyrolysis unit, the biomass feedstock can be heated and/orpyrolyzed in the closed pyrolysis unit to form pyrolysis products, andthen the pyrolysis unit can be opened for the removal of the pyrolysisproducts. The biomass feedstock can also be left in the pyrolysis unituntil it has been partially or fully pyrolysed and cooled down, withremoval of gas and vapor during pyrolysis; retention of all productsinside the reactor until it has cooled down, or partial removal of thegas and vapor products during the pyrolysis process.

The pyrolysis products can be a selected type of biochar core that areproduced from a predetermined biomass feedstock using a predeterminedset of pyrolysis conditions and optionally, secondary and/or tertiarytreatment of the resultant biochar. For example. Feedstock A that ispyrolyzed under conditions G produce biochar core X. Feedstock A can beformed from a variety of biomass materials, so long as the biomassmaterials produce a blend of materials that exhibit properties that arewithin a specified range for feedstock A. Based on the properties of thefeedstock, the conditions G are selected such that biochar core X willbe formed. For example, pyrolysis time or temperature can be increasedif tire water content of the feedstock is increased. Conversely,pyrolysis time or temperature can be decreased if the water content ofthe feedstock is decreased. Alteration of the pyrolysis conditions basedon the feedstock can allow for the production of biochar core X, whichexhibits selected properties. Under certain circumstances, a feedstockcan be chosen that does not fall within the specified range ofproperties for feedstock A. In this case, a biochar core that is notbiochar core X is formed.

The pyrolysis of a biomass material involves a wide range of parameters,relating to the feedstock and to the pyrolysis process:

Biomass Related:

intrinsic properties of the biomass (e.g., original lignin, cellulose,hemi-cellulose, ash content and composition and extractive)

biomass pretreatment (e.g., additives/ash content and concentration,moisture, chemical composition, changes in the proportions of lignin,cellulose, hemi-cellulose and extractives)

biomass degree of polymerisation

biomass density

biomass particle size

biomass particle shape

biomass physical and thermal properties (e.g., specific heat capacity,thermal conductivity, permeability)

Pyrolysis Reactor Operation:

reactor temperature

temperature at which pyrolysis occurs at lie surface of the particleand/or at the geometric centre of the particle to assess completeness ofpyrolysis

product reactor residence time in the reactor

product temperature in the reactor

biomass heating rate and heat transfer

biomass decomposition temperature or temperature range

pressure (e.g., hydrostatic and mechanical)

gaseous environment (e.g., gaseous environment in the reactor)

Recovery of the Final Products:

rate of thermal quenching of the products (e.g., char can be cooled withgas, liquid or solid)

time/temperature profile of the cooling of the bio char

One or more of these parameters, or any other parameters or conditionsdescribed herein, can be controlled to produce the biochar core productsdescribed herein. These parameters can be controlled to variable degreesand some parameters may have a greater influence on the properties ofthe pyrolysis products than others.

In some embodiments of the invention, materials can be fed to or removedfrom the pyrolysis unit under controlled conditions while the pyrolysisunit is operating. For example, syngas, bio-oil biochar core, or anycombination thereof produced during pyrolysis can be collected from thepyrolysis unit and used for heating of the pyrolysis unit, heat export,power generation or other applications including but not limited to thesynthesis of chemicals and derived products. Alternatively, a biomassfeedstock and/or with reagents can be added to the pyrolysis unit duringthe pyrolysis process. The pyrolysis unit can have a plurality ofstages. The pyrolysis unit can have a first stage for heating and/orpyrolyzing the biomass feedstock under a first set of conditions and asecond stage for heating and/or pyrotyzing the biomass feedstock under asecond set of conditions. The biomass feedstock can be transferred firstto the first stage and then to the second stage. Alternatively, thebiomass feedstock can be moved through the pyrolysis unit in acontinuous mode. The biomass feedstock can be pyrolyzed under aplurality of conditions as the biomass feedstock moves through thepyrolysis unit, or conversely retained in the unit until the processinghas been completed.

The pyrolysis unit can have one 01 more temperature sensors formonitoring and controlling the temperature of the biomass feedstockduring pyrolysis. The temperature sensors can be positioned throughoutthe pyrolysis unit such that the temperature sensors provide effectivemonitoring of the temperature of the biomass feedstock, the surfacetemperature of the biomass feedstock, and/or the environment surroundingthe biomass and/or reagents. Similarly, the pyrolysis unit can have oneor more pressure and/or oxygen sensors for monitoring and controllingthe amount of pressure and/or oxygen in the pyrolysis unit. The pressureand/or oxygen sensors can be spaced throughout the pyrolysis unit forappropriate monitoring of the pressure and/or oxygen levels in thepyrolysis unit. Other instrumentation can be added as required tomonitor and control the process.

Heat can be supplied to the pyrolysis unit using a variety of energysources and in a variety of ways (hot gases, molten salts, hot sand andfrom contact with heated metal surfaces, microwaves). For example,energy sources can be combusted for the formation of heat, which can betransferred to the pyrolysis unit. Alternatively, microwave energy canbe utilized for the pyrolysis of the biomass feedstock, as described inPCT Publication No. WO2008/079029, incorporated herein by reference inits entirety.

The pyrolysis unit can be operated under predetermined reactionconditions such that one or more selected pyrolysis products are formed.For example, the pyrolysis unit can be controlled such that a biomassfeedstock is heated at a specific rate to a desired temperature whilebeing exposed to a specified level of oxygen. The specific rate can beup to about, about, or less than about 0.01, 1, 10, 100, or 1000.degree.C. per second, which can be determined at the reaction interface. Thespecific rate can be controlled to within about or less than about 5,10, 20, or 40.degree. C. per second, which can be determined at thereaction interface or at the centre of the particle. The temperature ofthe biomass feedstock, which can be the final or peak temperature, canbe controlled to within about or less than about 100, 20, 10, or5.degree. C. The final temperature of the pyrolysed biomass can be atemperature up to about 200, 500, or 1000degree. C. The pyrolysis unitcan be controlled such that the biomass feedstock is held at specifictemperature for a desired amount of time. The time can be controlled towithin about or less than about 50, 5, or 0.5 minutes. The pyrolysisproducts can be formed within the pyrolysis unit in about, greater thanabout or less than about 0.001, 0.01, 0.1, 1, 2, 3, 4, 5, 6, 7, or 10days.

Some conditions for performing pyrolysis are described in PCT PatentPublication No. WO2009/016381, incorporated herein by reference in itsentirety. The pyrolysis or charring process can involve heating abiomass feedstock over 250.degree. C. under oxygen deficient conditionsleading to its decomposition. Thus, the absence of an oxidizing agent,such as an acid, steam or air may be preferred. The temperature willnormally be selected according to the substance to be charred and theextent to which it is desired to remove unwanted compounds (organic orinorganic) or other contaminants. The process may not need to be sealed,as the heated material can give off volatile products (condensable andnon-condensable). Air ingress to the pyrolysis unit can be minimized orobviated by the addition of inert gas purging (N.sub.2, Ar (or othernoble gas), combustion products (CO.sub.2, CO, H,sub.2O), steam orrestricting the ingress of air by operating the unit under a positivepressure). In some embodiments of the invention, pyrolysis conditionscan maximize production of energy in the form of a variety of products,such as syngas or Biooil.™., can maximize the production of a selectedtype of biochar, or can be optimized for a balance between energyproduction and biochar production. The selected type of biochar core canhave particular characteristics, as described herein.

Some pyrolysis processes can be classified as slow pyrolysis or fastpyrolysis. Slow pyrolysis can be performed at temperatures of between300 and 450.degree. C. Slow pyrolysis can involve heating biomassfeedstock at a temperature rate between about 0.1 to 50.degree. C. persecond. Fast pyrolysis can be performed at higher temperatures, whichcan be from 400-1000.degree. C, depending on whether liquids or gasesare to be optimized and/or the nature of the feedstock. Fast pyrolysiscan involve heating biomass feedstock at a temperature rate change,which can be determined at the reaction interface, between about 100 to1000.degree. C. per second. The yield of products from pyrolysis, and/orwhether or not the pyrolysis is fast or slow, can vary with temperature,feedstock composition and size/shape, residence time and heating rate.In some embodiments of the invention, increased amounts of chat can becreated per unit biomass at the lower pyrolysis temperatures. Hightemperature pyrolysis can produce greater amounts of syngas from thebiomass.

Fast pyrolysis, including fast pyrolysis of soft or hardwood particlesless than 6 mm in their maximum dimension at a reactor temperature of450-525.degree. C., can yield about 75% bio-oil (which may includereaction water), 14% biochar, and 11% syngas, and decomposition of thefeedstock can be completed in seconds. Slow pyrolysis can be optimizedto produce substantially more biochar (which can be up to −45-50 wt % ofthe dry ash free biomass) and can take on the order of hours tocomplete. In some embodiments, slow pyrolysis can be performed at highpressure.

The invention provides for methods for producing a biochar core that canhave particular carbon and/or volatile carbon content. Biocharexhibiting these particular properties can be produced using selectedpyrolysis conditions described herein. For example, a biomass feedstockis heated at a sufficiently slow rate and for a sufficient amount oftime such that volatile organics are allowed to escape from the biomassand do not recondense within the pyrolysis reactor. The volatileorganics can be removed from the pyrolysis reactor thereby preventingthe volatile organics from recondensing in the pyrolysis reactor or onthe pyrolyzing biomass. Alternatively, the reaction conditions can besuch that the volatile organics do not recondense in the pyrolysisreactor. In other embodiments of the invention, the reaction conditionscan be such that the volatile organics recondense in the pyrolysisreactor, and in some cases, on the biomass feedstock. The rate ofheating or the amount of heat applied can be such that the rate ofrelease of volatile organics is less than about, about, or greater thanabout 75, 50, 30, 20, 10, 5, or 1% per hour of the total volatileorganics present in the feedstock or that can be released by pyrolysis.The rate of heating or amount of heat applied can have multiple stages.For example, the rate of heating or amount of heat applied can be highand then low, or low and then high. In some embodiments of theinvention, the rate of heating or amount of heat applied can change on alogarithmic, exponential, or linear scale. An example of the range ofpossible values of pyrolysis conditions and properties of resultantchars, including amount of volatile products in chars, are given inTable 1.

TABLE 1 Properties of charcoal produced at various temperatures fromAcacia bussei produced in a muffle furnace Pyrolysis Fixed GrossCalorific Charcoal Energy Temp C H O^(a) Ash Water Volatiles CarbonValue yield^(b) yield^(c) [° C.] [wt %] [wt %] [wt %] [wt %] [wt %] [wt%] [wt %] [MJ/kg] [wt %] [%] 300 30.2 5.67 63.73 0.4 1.9 70.8 28.8 22.456.27 65.92 400 71.5 3.93 22.17 2.4 2.8 30.9 66.7 29.88 28.03 43.80 50087.0 3.10 8.50 1.4 2.8 17.7 80.9 32.14 22.65 38.07 600 87.5 2.67 6.932.9 1.0 7.1 90.0 33.20 21.63 37.56 700 92.4 1.71 3.89 2.0 1.8 3.9 94.133.40 20.16 34.22 800 93.4 1.03 3.57 2.0 2.2 2.4 95.6 33.90 19.54 34.64Notes: ^(a)assumes no Sulphur or nitrogen present ^(b)dry weight ofcharcoal divided by weight of wood ^(c)gross calorifie value of charcoalmultiplied by charcoal yield divided by gross calorific value of thewood. Reference: Hollingdale, A. C., Krishnan, R., Robinson, A. P.,“Charcoal Production A Handbook”. Chapter 2, Page 7, Eco-logic books,1999, ISBN 1 899233 05 9.

The biomass feedstock can be heated for enough time and under sufficienttemperature conditions that the biochar core product has a selectedand/or controlled carbon content. The carbon content can be greater thanabout, about, or less than about 10, 20, 40, 60, 75, 80, 90, 95, 97, 99,or 99.5 wt %. Hie carbon content can be measured as a portion of the dryweight of the bio char.

The biomass feedstock can be heated for enough time and under sufficienttemperature conditions that the biochar core product has a selectedand/or controlled volatiles content. The volatiles content can begreater than about, about, or less than 90, 80, 50, 30, 25, 20, 15, 10,5, 1, or 0.1 wt %. The volatiles content can lie measured as a portionof the dry weight of the biochar or the total weight of the biochar.

In some embodiments of the invention, the pyrolysis conditions can besuch that a selected biochar core having an elemental composition orphysical characteristic described herein. For example, the pyrolysisconditions can be such that biochar core has a selected content ofcarbon, nitrogen, oxygen, hydrogen, potassium, or phosphorous.Alternatively, the pyrolysis conditions can be such that the biocharcore has a desired cation exchange capacity, density, porosity, poresize, average pore size, crystallinity, size distribution, surface area,surface area per mass, or adsorption capacity.

In some embodiments of the invention, the conditions for pyrolysis caninclude a temperature heating rate that is less than about 53, 10, 5, 1,or 0.1degree. C. and a final temperature can of greater than about 500,600, 700, 800, 900, or 1000.degree. C.

In some embodiments of the invention, completion of the pyrolysisprocess is determined by monitoring the rate of release of compoundsfrom the biomass feedstock. Once the rate of release of compounds hasdecreased to about 0.5, 1.5, 10, 20, or 50% of the maximum rate ofrelease of compounds, the pyrolysis process may be deemed to havecompleted. The compounds that are monitored for release can bevolatiles, organic carbons, volatile organic carbons, volatile carbons,water vapor or organic volatiles and/or permanent gases such asCO.sub.2, CO, H.sub.2, CH.sub.4 and other higher hydrocarbons.Alternatively, the pyrolysis process can be performed until the biocharproduct formed has a volatile (volatile containing solid compounds,volatile organic compounds, or volatile carbon compounds) content ofgreater than about, about, or less than about 90, 80, 50, 30, 25, 20,15, 10, 5, 1, or 0.1 Wt %. The pyrolysis conditions can be such that theamount of volatiles in the biochar product can be controlled to within0.1, 1, 5, or 10 wt %. The amount of volatiles can be measured byanalysis of the composition of the biochar immediately after removalfrom the pyrolysis reactor or after post-pyrolysis treatment. In someembodiments, the percentage is determined as a percentage of total massof the biochar. In other embodiments of the invention, the percentage isdetermined as a percentage of non-volatile carbons.

The invention provides for use of the pyrolysis products for thepyrolysis process. For example, the invention provides for post-heatingmanagement of the pyrolysis products. Meat in the pyrolysis products canbe recovered and/or used for the heating and/or drying and/ortorrefaction of the biomass feedstock. Alternatively, the heat from thepyrolysis products can be used for the generation of energy. Forexample, heat from the pyrolysis products can be used to heat a steamgenerator for production of electricity or for activation of the biocharusing steam, CO.sub.2. or combination of thereof. In other embodimentsof the invention, pyrolysis products can be used for the generation ofenergy, which can be used to power the pyrolysis process. The inventionalso provides for a variety of methods and processes to modify thepyrolysis products, described herein.

III. Biochar Post-Pyrolysis Treatment

In some embodiments of the invention, the pyrolyzed biomass is subjectedto post-treatment. Post-treatment can be used to control thecharacteristics of the biochar core product, such that a specificbiochar core product is formed. Post-treatment can include solventwashing, high temperature heating, gasification, sorting, grinding,chipping, or chopping. For example, pyrolyzed biomass can be subjectedto an organic solvent wash to remove volatiles from the pyrolyzedbiomass. Alternatively, the pyrolyzed biomass can be sorted for size andor density, such that pyrolyzed biomass particles of a specified sizeand or density distribution are grouped together.

IV. Biochar Core

The biochar core produced using the methods, devices, and systemsdescribed herein can have selected properties that improve thefunctional characteristics of the biochar core in a variety ofapplications. These properties can include the elemental composition ofthe biochar core, such as carbon, total carbon, organic carbon, totalorganic carbon, nitrogen, oxygen, hydrogen, potassium, or phosphorouscontent and other non-specified elements. The selected content levels ofthese elemental compositions within the biochar core can be any leveldescribed herein. Other selected properties of the biochar core caninclude cation exchange capacity, density, porosity, pore size, averagepore size, crystallinity, size distribution, surface area, surface areaper mass, or adsorption capacity. The porosity can be a fraction of thetotal volume greater than about, about, or less than about 0, 0.1, 0.2,0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0. The pore size or average poresize can be in the range of 5 to 50 .mu.m. The pore size or average poresize can be greater than about, about, or less than about 0.01, 0.1, 1,5, 10, 25, 50, 100, 200, 400, or 1000 .mu.m. The surface area can begreater than about, about, or less than about 1, 50, 100, 300, 500, 750,1000, 2500, or 5000 m.sup.2 per gram.

The biochar core properties can be selected such that the biochar coreis stable, inert and/or exhibits reduced degradation over time. Thedegradation of the biochar core can be through biotic, abiotic, chemicalor oxidative reactions. The degradation can be measured by determiningthe amount of carbon in the biochar core as a percent of initial carbonin the biochar core after pyrolysis. The carbon can be organic carbon,inorganic carbon, or both inorganic and organic carbon. The rate ofdegradation can be about or less than about 20, 15, 10, 5, 2.5, 1, 0.5,or 0.1% per year. The rate of degradation can be measured over a timespan of 1, 2, 5, or 10 years or longer. Alternatively, the rate ofdegradation can be measured over one, two, or three months in the first,second, third, fourth, or fifth year after production of the biocharcore or after use of the biochar core for a particular purpose. Theparticular purpose can be use of the biochar core as a soil amendment,fertilizing agent, microbial delivery agent, or any other purposedescribed herein.

The rate of degradation can be controlled by selection of the propertiesof the biochar core. For example, the biochar core produced using themethods described herein can have a low volatile organic carbon contentand/or a highly sable non-volatile component. This can reduce the degreethat the biochar core can be degraded by microbial organisms that mayutilize the biochar core as an energy or nutrient source. In someembodiments of the invention, the biochar core can have a controlledrate of degradation based on the form of carbon in the biochar core.These forms can include any of the forms described herein, and can beselected by a variety of parameters, including the type of biomass feedmaterial. In other embodiments of the invention, post-pyrolysistreatments, such as annealing, can be used to control the rate ofdegradation of the biochar core. The biochar core can be produced suchthat it has a high carbon content and can easily degrade or be stable.

V. Biochar Functionalization

The biochar core and/or enhanced biochar core can be functionalized orprocessed by a variety of methods to form a functionalized biochar. Forexample, the biochar core can be sorted, chemically or physicallytreated, or supplemented with nutrients, chemicals, or organisms. Insome embodiments of the invention, the biochar core can be sorted bysize or density such that biochar core particles of a particular sizedistribution or density are grouped together. Alternatively, the biocharcore can be treated chemically and/or physically to form a biochar withactivated carbon. The activated carbon can have an increased surfacearea, porosity, water retention, or cation exchange capacity that allowsfor improved functional activity of the biochar core. For example, thebiochar with activated carbon can have increased capacity to holdnutrients or microbial inoculants.

In some embodiments of the invention, the biochar core or activatedbiochar core are mixed or blended with a supplement. The supplement caninclude inorganic chemicals such as fertilizers and nutrients.Alternatively, the supplement can organic materials with properties thatincrease the CEC, nutrient content or performance of biochar as amicrobial habitat or it may be organisms such as fungi or bacteria orcombinations of thereof.

The chemicals that can be mixed with the biochar core include nitrogen,phosphorous, potassium, calcium, sulphur, and magnesium sources. Thesources can be in the form of fertilizer, compost, manure, ammonia,ammonium nitrate, urea, lime, limestone, rock phosphate, salt peter,gypsum, crop or other inorganic and organic compound containing theseelements.

The biochar products can be supplemented with nutrient sources or othermaterials, such as those described herein, to form a biochar productwith a known, desired, or selected amount of nutrients or othermaterials.

Organisms that can be supplemented to the biochar core can include fungiand bacteria. In some embodiments of the invention, the biochar core canbe supplemented with trichoderma. Examples of trichoderma are discussedin U.S. Pat. No. 6,060,507, incorporated herein by reference in itsentirety.

Other organisms can include Accumulibacter phophatis, Anabaena, Azolla,Bacillus circulans, Bacillus subtilis var natto, Bifidobacteriumanimalis, Bifidobacterium bifidum, Bifidobacterium longum, Deinococcusradiodurans, Lactobacillus acidophilus, Lactobacillus buchneri,Lactobacillus bulgaricus, Lactobacillus casei, Lactobacillusdelbrueckii, Lactobacillus plantarum, Lactococcus diacetylactis,Lactococcus lactic, Mycorrhiza, Pseudomonas aeruginosa, Pseudomonasputida, Ralstonia metallidurans, Rhizobia, Rhodobacter, Rhodopseudomonaspalustris, Rhodopseudomonas sphaeroides, Saccharomyces cerevisiae,Streptococcus thennophilus, Ulocladium oudemansii or Xanthamonasmaltophilia. Tlte rhizohacteria can be a rhizobium plant growthpromoting rhizohacteria Combinations of these organisms can besupplemented to a biochar core. A combination of organisms can be chosenbased on the symbiotic relationships between organisms and the desiredfunctionality of the biochar core. For example, thiobacteria can besupplemented to a biochar core for forming a bioremediation agent. Insome embodiments, beneficial bacteria can be supplemented to a biocharcore.

Organisms that can be supplemented to the biochar core can be organismsthat have been identified as an efficient microorganism. These organismscan control the growth of fungus or other adverse species.Alternatively, these organisms can be used for the generation ofnutrients that are beneficial to the grow th of particular organisms,such as plants. For example, some organisms can be used to increase therate of nitrogen fixation in soil. The biochar can be produced such thatis has an architecture is desirable as a habitat for one or moreorganisms, sugars and nutrients can be supplemented to facilitate adesirable habitat. The biochar can be packed in a way that ensuresviability of the one or more organisms, which may be inoculants.

The organisms can be added to the biochar core along with nutrients thatmay allow the organisms to remain viable until the biochar is applied toa particular site. In other embodiments of the invention, organisms canbe added to the biochar core without nutrients or selected nutrients orwith or without organic supplements. The functionalized biochar can bedesigned such that a sufficient amount of colony-forming units of anorganism are present upon application of the functionalized biochar to asite for inoculation by the organism.

In other embodiments, the invention provides for a method to alter theeffective cation exchange capacity of biochar. A biochar core can bemixed with organic materials to alter the CBC of the resultant product.A biochar or biochar core can be leached with solutions containingacids, such as humic acids, fulvic acids, or any combination thereof.The acids can be solid humic acids, solid fulvic acids, or anycombination or blend thereof.

The invention also provides for methods for changing the pH and/or limeequivalency of biochar. Biochar productions methods can include a postpyrolysis step of adding chemicals to immediately lower the pH ofbiochar. In other embodiments, the post pyrolysis step can includeblending biochar with organic matter materials to either increase ordecrease the pH of the resultant mixture. The post pyrolysis step caninclude adding elements and chemicals to lower the pH of biochar overtime. The post pyrolysis step can include blending biochar with organicmatter materials and chemicals to either increase or decrease the pH ofthe resultant mixture.

The post pyrolysis step can include adding elements and chemicals toincrease the pH of biochar. The chemicals used to adjust the pH of diebiochar can include A1SO.sub.4 and sulfur-based acids or bases. The pHcan be adjusted to be about, less than about, or greater than about 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,13, or 14. The pH adjusted biocharcan maintain its adjusted pH for a period of at least 0.5, 1, 2, 3, 4,5, or more years. For example, FIG. 3 shows the effect of usingA1SO.sub.4 to treat biochar (series 1), biochar blended with green waste(series 2) and composted dairy manure (series 3). The pH was measured 5days after amendment. In FIG. 3. the x-axis indicates the amount ofA1SO.sub.4 used, where 1 corresponds to 0 grams. 2 corresponds to 2.5grams, 3 corresponds to 5 grams, 4 corresponds to 10 grams, and 5corresponds to 20 grams. As can be observed, the pH of the biochar canbe readily adjusted by using varying amounts of A1SO4. The composts andbiochar can be form from food waste, such as food scraps, compostableplates, which can be mixed with yard and wood waste. The materials canbe ground using a tub grinder prior to composting. The composts andbiochar can be screened to pass a 6 mm sieve prior to mixing.

The pH measurement can be measured using a saturated media extract.Water can be added to saturate the growing media and the growing mediacan be allowed to equilibrate for 2 hours. Then, approximately 50 ml ofadditional water can be added and the displaced solution can becollected over a 10 minute period. The pH and/or electrical conductivitycan be measured on this collected.

VI. Biochar Porosity

The methods described herein provide for a method for altering theporosity and/or water holding characteristics of biochar. In someembodiments, methods for altering porosity and or water holdingcharacteristics include mixing biochar post pyrolysis with wettingagents. Other embodiments provide for extended heating or annealing toremove pyrolysis liquids from biochar core and to remove materials thatcause hydrophobicity. The biochar can be blended with organic materialsto deliver blended products with defined porosity and water holdingcharacteristics. FIG. 4 is a graph showing the modification of varioustypes of biochar using a wetting agent. Biochar was produced fromsoftwood chips having approximately 25-30 mm max diameter and a moistureof 10-20% on a dry weight basis. In FIG. 4, the biochars B1, B2, and B3were produced according to the following heating temperatures andresidence times: B1—600.degree. C. (range 580-600.degree. C.), Residencetime of 50 minutes; B2—500.degree. C. (range 480-520.degree. C.),Residence time 50-60 minute; and B3—400.degree. C. (range 380 to430.degree. C.), Residence time 67 minutes. The wetting agents used werethe following: WA0-distilled water; WA1-12.50 mL wetting agent/L water;WA2-25.00 mL wetting agent/L water; and WA3-50.00 mL waiting agent/Lwater; 5 ml of WA0, WA1, WA2. respectively, was added 39 cubic inches ofbiochar. The wetting agent was Aquatrols AG2000, which comprises 99%Non-Ionic surfactant, <1% water. <0.0025% Ethylene Oxide, and <0.002%Dioxane.

The y-axis depicts g of H.sub.2O/g of media (or biochar or biocharblend). Water retention was measured as g of w ater retained/g sampleafter a saturated sample w as allowed to drain for approximately 12hours. As can be observed from FIG. 4, the water retentioncharacteristics of the biochar or biochar blend can be readily adjustedto be significantly higher or lower than currently available products,allowing for greater control over soil moisture conditions and higheryield of the soil. In some embodiments, the biochar or biochar blend canhave a water retention of at least about, about, or less than about 0.1,0.2, 0.3, 0.5, 0.75, 1, 1.25, 1.5, 1.75, 2, 2.5, or 3 g of water/g ofbiochar or biochar blend. In some embodiments, the biochar or biocharblend can have a water retention of between about 1.5 to 2.5 g ofwater/g of biochar or biochar blend.

The methods described herein also provide for a method to alter theporosity, water holding and physical characteristics of growing media.The invention provides for a method of including selecting feedstock andpyrolysis conditions to influence the porosity of biochar. In someembodiments, biochar size characteristics are altered post pyrolysis bymechanical means. The particle size of biochar can be altered bypre-pyrolysis processing of feedstock.

FIG. 5 shows a graph of biochar compositions (Poultry biochar. Blend 1,Blend 2. Blend 3, and Blend 4) having varying aeration and water holdingcharacteristics, along with the aeration and water holdingcharacteristics for Mode Grow, MSC (Mulch and Soil Council) Control,Westside peat mix. By controlling proportions of biochar in blends andselecting blending materials we can produce products with a wide rangeof total porosity with different aeration, and water holdingcharacteristics.

Biochars described herein can have a selected total porosity and waterholding capacity. The total porosity can be about, less than about, orgreater than about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55,60, 65, 70,75, 80, 90 or 95%. The aeration can be about, less than about, orgreater than about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65,70, 75, 80, 90 or 95%. The water holding capacity can be about, lessthan about, or greater than about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50,55, 60, 65, 70, 75, 80, 90 or 95%. In some embodiments, the waterholding capacity can be increased, to effectively create a reservoir ofplant available water), while maintaining an air filled porosity thatallows air to reach the plant roots. This increased control over othersoil amendments allows for improved soil performance, includingincreased plant growth and/or yield.

To determine aeration, total porosity and water holding characteristics,a known volume of a sample, such as soil, growing media, or biochar canbe placed in a pvc cylinder with a drilled cap on the base. The holescan be covered, and then the sample can be saturated with water. Oncesaturated, the sample can be weighed again. The weight of water in thesample (W1) added represents the total porosity in the soil. The drainholes can be unblocked and the soil can be allowed to drain overnight(approx 12-16 hours) and the water can be weighed again (W2). W2represents the water holding capacity and W1-W2-air filled porosity oraeration. In FIG. 5, the air filled porosity/aeration and water holdingcapacity are expressed as percentages, as determined by the following:aeration=(W1-W2/(W1+sample weight); water holding capacity=W2/(W1+sampleweight).

VII. Biochar Applications

The methods of the invention provide for the use of biochar for avariety of purposes. The biochar can be used as a soil amendment,potting mix, a substitute in a growing media (including peat and/orcompost media), a horticultural media, a carbon sequestration agent, afertilizing agent, a turfgrass establishment, a bioremediatiou agent, adelivery agent for a fungi or bacterial population, a synthetic “terrapreta” (or equivalent material) or any combination thereof.

In some embodiments of the invention, the biochar is used for carbonsequestration by fixing of carbon in the soil in a recalcitrant form. Anexample of the use of biochar for carbon sequestration is described inU.S. Patent Application No. 2004/0111968, incorporated herein byreference in its entirety. When the biochar is used for carbonsequestration, the biochar core is selected to have resistance todegradation, as described herein. The time scale for the biochar corecan be greater than about, less than about, or on the order of hundredsof years.

In other embodiments of the invention, biochar or an enhanced and/orfunctionalized biochar can be used for mitigation of soil greenhouse gasemissions. For example, an enhanced and/or functionalized biochar can beused to reduce emission of methane or nitrogen containing gases, such asnitrous oxide.

In other embodiments of the invention, the biochar is used for on-demandrelease of chemicals or other materials. These chemicals can befertilizers, nutrients, or other materials that are depleted over timeat a particular site. The chemicals can also be chemicals that create aprotective environment for a desired organism to be grown, e.g.,pesticides or insecticides or other chemicals that may attract orsupport beneficial organisms. The fertilizers, nutrients, or othermaterials can be depleted by organisms such as plants and microbes. Thechemicals can be released from the biochar based on the concentration ofthe fertilizer, nutrients, or other materials in the surroundingenvironment. The release of the chemicals can be such that theconcentration of the chemical in the surrounding environment ismaintained at a relatively constant level.

The biochars described herein can be used to enhance agriculturaloutput, horticultural qualities, or turf grass. For example, biocharscan be used to improve the yield of an agricultural crop and/or toimprove the resistance of the crop to detrimental environmental effects.Detrimental environmental effects can include harmful organisms, e.g.,harmful fungi or insects, diseases, drought, low water, heat, wind,cold, frost, pollution, saline-containing water, and polluted water. Insome embodiments of the invention, the biochars described herein canimprove water retention, drainage, aeration, or the effects ofcompaction. In other embodiments of the invention, the biochars can beused to improve crop quality or nutritional value. Blends of organism,nutrient, and biochar can be used to form “terra preta” soil. Adiscussion of terra preta can be found in PCT Publication No. WO2009/021528 and U.S. Patent Publication Nos. 2004/0111968 and2007/0148754, each of which are incorporated herein by reference. 10099jThe biochars described herein can lead to increased crop yield, loweruse of water or irrigation, less nutrient run-off, reduced fertilizeduse and cost, reversed soil degradation, and elimination, reduction, oravoidance of GHG emission from soil.

The biochars that can be produced using the methods and systemsdescribed herein can be used to reduce pollution in water run-offstreams and also to improve retention of water. The biochars can be usedto remove phosphorous and nitrogen compounds from water streams or fromother sources. The biochars can be used to protect ground water andother water bodies from undesired effects. For example, biochar can bedistributed at an agricultural site or a farming location such thatrunoff or other undesired materials do not contaminate the ground wateror other bodies of water.

FIG. 6 shows a graph of the capacity of biochar compositions in removingnutrients from a solution relative to composted dairy manure and manureand perlite, measured as electrical conductivity (mS) in leachatesamples of a composted manure and a sample of the manure mixed withbiochar and an inert material (perlite). The electrical conductivity isan indication of the nutrient salts in the leachate. Three treatmentswere used. Treatment 1 was Equal volumes of manure alone, Treatment 2 isManure plus biochar (50% by volume) and Treatment 3 is Manure plusperlite (50% by volume). As shown by FIG 6, biochar is more effectivethan the inert material in removing nutrients from solution. Treatment 1and 3 reflect the displacement of manure by the inert material (i.e.,dilution).

In some embodiments of the invention, a biochar is produced that can beused for bioremediation. The biochar can be designed to absorb toxicchemicals or have organisms that can convert the toxic chemicals to lessharmful chemicals. Examples of using biochar for bioremediation arediscussed in PCX Publication No. WO 2009/016381, incorporated herein byreference in its entirety.

The invention provides for a method to reduce the leachableconcentration of nutrients in nutrient rich wastes. In some embodiments,a biochar core is mixed in defined quantities with composted animalmanures to reduce the leachable nutrient concentration of thosematerials. A biochar core can be mixed in defined quantities withnutrient rich composts to reduce the leachable nutrient concentration ofthose materials. A biochar core can be mixed in defined quantities withnutrient rich wastes to reduce the leachable nutrient concentration ofthose materials.

In other embodiments, the invention provides for a method to modify theavailability of phosphorus. A biochar core can be selected for itsability to interact directly or indirectly with inorganic phosphorus ororganic phosphorus, modifying the availability of phosphorus to growingplants. A biochar core can be used to modify the availability ofphosphorus in nutrient rich organic waste streams. In some embodiments,inorganic or phosphorus rich organic materials sources are blended withbiochar core and other organic materials to create with specifiedavailability of phosphorus to growing plants.

In other aspects, the invention provides for a method to modify theavailability of nitrogen. A biochar core can be selected for its abilityto interact directly or indirectly with inorganic nitrogen sources,modifying the availability of nitrogen to growing plants. Inorganicnitrogen sources can be added to a biochar core as a solution modifyingthe availability of nitrogen to growing plants. Inorganic nitrogensources can be blended with biochar core to modify the availability ofnitrogen to growing plants. Inorganic nitrogen sources can be blendedwith biochar core and organic materials to create biochar with specifiedavailability of nitrogen to growing plants.

Nitrogen and/or phosphorus rich waste materials can be mixed with abiochar or mixed with an organic matter to be pyrolyzed, which thenforms a biochar with a selected phosphorus and/or nitrogen availability.Phosphorus rich wastes can include poultry litter and cattle wastes (drybedded manures) and solids from anaerobic digestion. The waste can bepyrolysed and the nutrients, such as phosphorus and nitrogen, can bewithin the biochar as salts or in the organic structures themselves ofthe biochar.

Additionally, the biochar can be mixed with coconut coir, aged pinebark, redwood, or other carbon sources. In some embodiments thesaturated media extract can have a reduced salt concentration. This canbe measured in terms of electrical conductivity, and in a saturatedmedia extract the electrical conductivity can be about 1.5-5.0 Ms/cm.Additional nutrients may then be added to balance the nutrientcomposition in the media. In some embodiments the available phosphorusand/or nitrogen can be characterized as the phosphorus and/or nitrogenthat is in a specified chemical form or the types of phosphorus and/ornitrogen that can be metabolized by a plant, fungus, or any othergrowing organism. In some embodiments, the available nutrients, such asavailable phosphorous and-or available ritrogen, are those that can bemetabolized by a plant. For example, available phosphorus may be inphosphorus in the form of orthophosphates and available nitrogen can benitrogen in the form of nitrates, ammonium or ammonia.

The amount of total phosphate or nitrogen in the biochar or biocharblend, as measured on a phosphate or nitrogen basis per amount ofbiochar or biochar blend, can be about, less than about, or greater thanabout 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 10, 50, 100,500, 1000, or 1500 mg/mL. The amount of total phosphate or nitrogen, asmeasured on a phosphate or nitrogen basis per amount of biochar orbiochar blend, can be about, less than about, or greater than about 1,2, 3, 4, 5, 10, 20, 30, 40, 50, 75, 100, 200, 300, 400, 500, 600, 750,1000, 2000, 30000, 5000, 7500, 10000, 50000, 100000, 250000, 500000, or1000000 ppm. The amount of total phosphate or nitrogen, as measured on aphosphate or nitrogen basis per amount of biochar or biochar blend, canbe between about 50-100, 500-1000, 5-1000, 50-10000, 150-1000,1500-10000, 15-10000, 150-100000, 10-250000, or 1-2500000 ppm. Theamount of total phosphate in the biochar or biochar blend can be betweenabout 50-100 or 500-1000 ppm. The amount of total nitrogen can bebetween about 150-1000 or 1500-10000 ppm.

The nutrient content and formulation in the biochar or biochar blend canbe selected such that the total phosphorus or nitrogen in the biochar orbiochar blend, which can be used as a soil amendment, can be 1, 1.5, 2,2.5, 3, 5, 6, 10, 20, 50, 100, 200, 300, 500, or 1000 times greater thanthe amount of available phosphorus or nitrogen provided by a biochar orbiochar blend. The total phosphorous and/or total nitrogen may begreater than the available phosphorous and/or available nitrogen byincluding organic forms of nitrogen and phosphate that may not bedirectly metabolized by a plant or any other specific organism.

The amount of available phosphate or nitrogen contained in the biocharor biochar blend, as measured on a phosphate or nitrogen basis peramount of biochar or biochar blend, can be about, less than about, orgreater than about 0.001, 0.005, 0.01, 0.05, 0.1.0.5, 1, 2, 3,4, 5, 10,50, 100, 500, 1000, or 1500 mg/mL. The amount of available phosphate ornitrogen contained in the biochar or biochar blend, as measured on aphosphate or nitrogen basis per amount of biochar or biochar blend, canbe about, less than about, or greater than about 1, 2, 3, 4, 5, 10, 20,30, 40, 50, 75, 100, 200, 300, 400, 500, 600, 750, 1000, 2000, 3000,5000, 7500. 10000, 50000, 100000, 250000, 500000, or 1000000 ppm. Theamount of available phosphate or nitrogen contained in the biochar orbiochar blend, as measured on a phosphate or nitrogen basis per amountof biochar or biochar blend, can be between about 50-100, 5-1000,150-1000, 15-10000, or 10-250000 ppm.

The amount of available phosphate provided by the biochar or biocharblend in the biochar or biochar blend can be between about 10-500,25-250, or 50-100 ppm, as measured from extraction of a saturatedsolution exposed to the biochar or biochar blend. The amount ofavailable nitrogen provided by the biochar or biochar blend can bebetween about 50-5000, 100-2500, or 150-1000 ppm, as measured fromextraction of a saturated solution exposed to the biochar or biocharblend. In some embodiments, it may be desirable to control the nitrogenand phosphorous levels to be within a selected range so as to supportplant growth,

The phosphorus and/or nitrogen availability can be selected such that amicrobial biomass can be supported. The microbial biomass can providefor an effective slow release of phosphorus and nitrogen to plants. Bybalancing currently available phosphate and nitrogen sources with otherphosphate and nitrogen sources that can be metabolized by microbes, thebiochar or biochar blend can achieve desired nitrogen and phosphaterelease profiles.

In other embodiments, a biochar composition can have a selectedphosphorus and/or nitrogen availability that is effective at apredetermined time period, for example within one year or after 1, 2, 3,4, 5 or more years. The biochar composition can have a phosphorusavailability that is expressed relative to a conventional phosphorusavailability.

The invention provides for a method to reduce the carbon footprint ofcom based ethanol by using crop residues and by-product of manufactureto sequester carbon and produce energy. In some embodiments,predetermined set of operating parameters for producing a biocharinclude a time-dependent temperature profile to produce a biochar corewith a specified rate of degradation. The rate of degradation can be anydegradation rate described herein. For example, the rate of degradationmay be about or less than about 20,15, 10, 5, 2.5, 1, 0.5, or 0.1% peryear. The rate of degradation can be measured over a time span of 1, 2,5, or 10 years or longer. In other embodiments, a biochar core can beused to reduce the carbon emissions associated with the production ofcorn based ethanol.

The invention provides for a method to reduce the carbon footprint ofsugarcane based ethanol by using crop residues and by-product ofmanufacture to sequester carbon and produce energy. A predetermined setof operating parameters for producing biochar can include atime-dependent temperature profile to produce a biochar core with aspecified rate of degradation. The rate of degradation can be anydegradation rate described herein. For example, the rate of degradationmay be about or less than about 20, 15, 10, 5, 2.5, 1, 0.5, or 0.1% peryear. The rate of degradation can be measured over a time spar of 1, 2,5, or 10 years or longer. The biochar core can be used to reduce thecarbon emissions associated with the production of sugarcane ethanol.

In some embodiments, biochar can be used to reduce nutrient pollutantsin nutrient rich wastes. The nutrient rich waste can be in a landscapesetting. Biochar can be used to retain nutrients in a wet pond. Biocharcan be incorporated into the construction of a vegetated swale. Biocharcan be incorporated in soil and other materials used to create avegetated buffer strip. Biochar can be incorporated in the materialsused in the manufacture of a constructed wetland. Biochar can beincorporated as part of a vegetated rock filter. Any of the biocharsdescribed herein can be used for bioretention.

In some embodiments, a biochar can be used to increase soil pH. Thebiochar can be used as a liming substitute. A biochar can be used as asubstitute for lime in agricultural soils. A liming equivalency ofbiochar is established. Feedstock selection and pyrolysis conditions canbe optimized to deliver desired liming equivalency. Biochar can beprepared for incorporation in soil in order to maximize the benefit ofsoil pH adjustment, particle size slurrying, blending with othermaterials that can be used to raise soil pH. Biochar can be incorporatedin soil to adjust soil pH. In some embodiments, biochar can be used as asubstitute for lime in horticultural growing media. Biochar can beincorporated in to growing media to alter the pH of the growing media.

The invention also provides for a method where thermal treatment bypyrolysis is used to reduce odor in poultry wastes. Bedding materialscan be selected to influence the performance of pyrolysis to create anon odorous biochar. Pyrolysis process conditions can be optimized toreduce die odor of the biochar product.

In some embodiments, biochar can be treated post pyrolysis throughheating to modify characteristics such as porosity and hydrophobicity.In some embodiments, equipment can be used to alter the particle sizeand particle size distribution. Materials can be introduced to biocharto reduce dust and improve handling. Biochars can be blended with one ormore other materials, as described herein.

The invention provides for biochar delivery systems. These systems canbe used to improve the efficiency of water use in raised bed growingsystems. The biochar or a biochar blend, such as biochar mixed withanother component, can be used with raised bed growing systems thatutilize surface or subsurface irrigation systems to deliver water andnutrients. Biochar can be distributed uniformly within a bed in order tomodify the water holding and water release characteristics of die soil.Alternatively, biochar or a biochar blend can be distributednon-uniformly within a bed in order to modify the water holding andwater release characteristics of the soil.

The biochar can be positioned to intercept both water and nutrients thatare applied to soil irrigation systems. The biochar can be layeredabove, below, and or to the sides of the subsurface. The biochar can bepositioned less than, greater than, or at about 1, 2, 3, 4, 5. 6, 7, 8,9, 10, 15, 20, or 30 inches front the subsurface irrigation system. Thebiochar can be in a layer that is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 inchesthick, litis layer may comprise of biochar alone, or mixed with soil ororganic amendments. As shown in FIG. 7, the biochar or biochar blend canplaced in a zone around the irrigation tape or system, or the tape orsystem may be installed over a bed of biochar or the biochar may beincorporated in zones to each side of the tape or system. The zone canbe a concentric ring about the irrigation tape that is about, less thanabout, or at least about 1, 2 3, 4, 5, 6, 7 or 8 inches thick. As shownin FIG. 7, two irrigation tapes or systems, which may be parallel, canbe installed at or near as soil surface and a zone of biochar or biocharblend can be positioned around and below the irrigation tapes orsystems. The irrigation tapes or systems can be separated by about 5,10, 15, 20, 30, 40, or 50 inches. The tape or system may be installedfirst and, afterward, the biochar or biochar blend can be placed alongthe tape or system.

The invention also provides for a method to modify the availability ofnutrients applied through irrigation in raised bed growing systems.Biochar can be distributed uniformly within a bed in order to modify theavailability of fertilizer nutrients applied to the bed. Alternatively,biochar can be distributed non-uniformly within a bed in order to modifythe availability of fertilizer nutrients applied through buriedirrigation systems in the bed.

In some embodiments, biochar can be used to reduce nitrous oxideemissions, which may be from soil. In some embodiments, use of biocharcan allow for reduced usage of nitrogen fertilizer. This can be bycontrolling nitrogen availability, as described herein. The biochar canthen be used to increase the unit of harvested product per unit nitrogeninput or nitrogen fertilizer used. In other embodiments, biochar can beused to reduce nitrous oxide emissions from compost. In someembodiments, biochar is used to reduce indirect nitrous oxide emissionsthat result from the nitrification and subsequent denitrification ofnitrate that has been leached from soil. Biochar can be incorporated ingreen waste compost to reduce emissions of nitrous oxide.

In other embodiments, the invention provides for a method to influenceplant growth through signaling mechanisms. A pyrolysis process used toproduce biochar can be optimized to produce organic compounds thatstimulate plant growth. In some embodiments, biochar can be used tointerrupt signaling mechanisms used by competing plants to regulategrowth.

While preferred embodiments of the present invention have been shown anddescribed herein, it will be obvious to those skilled in the art thatsuch embodiments are provided by way of example only. Numerousvariations, changes, and substitutions will now occur to those skilledin the art without departing from the invention. It should be understoodthat various alternatives to the embodiments of the invention describedherein may be employed in practicing the invention. It is intended thatthe following claims define the scope of the invention and that methodsand structures within the scope of these claims and their equivalents becovered thereby.

We claim:
 1. A method for preparing a soil amendment comprising:providing a biomass to a pyrolysis unit; pyrolyzing the biomass in thepyrolysis unit to produce a stable biochar core that has a rate ofdegradation that is less than 2.5% per year; and using the stablebiochar to form a soil amendment for placement in a soil bed, whereinthe soil amendment has a selected total phosphorus and a total nitrogencontent and the soil amendment provides a selected concentration ofavailable phosphorus and available nitrogen.
 2. The method of claim 1,wherein the available phosphorus provided by the soil amendment isbetween about 5-1000 ppm and the available nitrogen provided by thebiochar is between about 15-10000 ppm.
 3. The method of claim 1, whereinthe soil amendment has a selected air filled porosity that is greaterthan about 10% and a selected water holding capacity that is greaterthan about 20%.
 4. The method of claim 1, wherein the biomass ispyrolyzed under (i) a heating rate between about 0.1.degree. C./secondand 50.degree. C./second, (ii) a temperature greater than about250.degree. C., and (iii) a heating time greater than about
 0. 1 days.5. The method of claim 1, wherein the biochar core is treated with awetting agent.
 6. The method of claim 1, wherein the biochar core ismixed,with soil or with coconut coir to form the soil amendment.
 7. Themethod of claim 1, wherein the biochar is pH adjusted to a pH less thanabout 6 using A1SO.sub.4.
 8. The method of claim 1, wherein the soilamendment is used in conjunction with an irrigation system.
 9. Themethod of claim 8, wherein the soil amendment is positioned in a layerthat is about 3 inches away from an irrigation system.
 10. The method ofclaim 8, wherein the soil amendment is positioned below an irrigationsystem in a layer that is about 4 inches thick.